2-hydroxyethyl 2-phenylethyl sulfide as a fungicide



I This invention relates Patented June 16, 1953 '1; i: ."at 21:":

zrlfi'lifiokfliim .Z- PHENYLETHYL sUL- FIDE ASfA FU NQICIDE I I JoachimDazzi, Dayton, Ohio, assignor to Monsanto Chemical Company, .St. Louis,Mo., a, corporation of Delaware No Dl-awing. Application March 25,1950,

Serial No. 151,994 a provements biological toxicants tion further'rlat'estt methods o'f'treating plants and other organic materials whichare subjectto attack by fu'n gj I have found that unusually efl'ectivTungicidal compositions are obtained when the active ingredient of suchcompositions is a compound having the general structure:

@CHMHMCHQMH to .new'and useful im- The inven- 2 Claims; et- 2.

in which R. is a member of the group consisting of hydrogen, chlorine,bromine and fluorine and n is an integer of from 2 to 4.

Compounds having the above general formula include the w-hydroxyalkylz-phenylethyl sulfides having the general structure:

Qomcmswmhon in which n is an integer bf from 2 to 4; and derivativesthereof having the general formula:

CHzCH2S(CH2)nOH in which X is a member of the group consisting ofchlorine, bromine, and fluorine and n is an integer of from 2 to 4. Asillustrative of compounds having the above general formulas may bementioned 2-hydroxyethyl 2-phenylethyl sul fide, 3-hydroxypropyl2-phenylet-hyl sulfide, 4- hydroxybutyl Z-phenylethyl sulfide,2-hydroxyethyl z-( l-chlorophenyl) ethyl sulfide, 3-hydroxypropyl2-(3-brom0phenyDethyl sulfide, 2-hydroxyethyl 2- (4-fluorophenyDethylsulfide, 4-

hydroxybutyl 2-(2,3-dich1orophenyl)ethyl sulfide, etc. These compoundsare readily obtainable by reaction of styrene or its nuclear monoordi-chloro, bromo, or fiuoro derivatives with mercapto alcohols producedby the addition reaction of hydrogen sulfide and an alkylene oxide,

e. g., ethylene oxide, methylethylene oxide, propylene oxide or butyleneoxide in known manner; e. g., as described in the British Patent No.532,676 issued to J. G. Fife. The compounds are highly efficient forpreventing and retarding fungus growth on plants, fruits, seeds, soils,fur,

leather, cotton, wood and organic materials in general. They may beapplied directly to the organic material which is to be treated, butbecause the present sulfides .tremely dilute 'concentrations, it ispreferred to incorporate the presentagentswi'tha carrier or 42-hydroxyethyl tested against Aspergillus niger usingthe followingtesting procedure:

diluent. I

[Fungicidal dustsmaybe preparedby mixing the: presentsulfidesrwithdusting materials such as talc, clay, lime, bentonite,pumice, fullers earth, etc. The present sulfides are soluble in theusual organic solvents and may be used in solution, e. g., in ethanolsolution as fungicidal sprays. Suspensions or dispersions ofthe-sulfides in a non-solvent such as water are advan' tageouslyemployed in the treatment of plant foliage, textiles, leather and othermaterials with which it is not desirable to employ either a solidcarrier or an organic solvent. I

Fungicidal. compositions comprising the pres-, ent active ingredientsmaybe applied only to the surface of the material to be treated as whentreating foliage, furs, leather and other compara tively impregnablematerials upon which fungus growth is to be prevented or retarded. Inother cases, for example, when it is desired to protect 1 seeds fromsoil microorganisms harmful to the seeds and plants, thehydroxyalkylphenylethyl Example 7 z-phenylethyl sulfide was Preliminary. 'IrommelsMalt Agar was poured intoaPetri plate and allowed to harden. A- circularsection was cut from the center and into this cup was The plate was thensprayed with ous spore suspension of Aspergillus cubated at atemperature of 28 a fresh aquem'ger and in! C. for five days.

1 Inspection of the incubated plate at the end of that time showed nowithin a 5 mm. zone.

Secondary.-To cc. of hot Trommels Malt Agar was added 0.1 gram of thepresent sulfide. The agar was then whipped into an emulsion and pouredinto a cold plate and allowed to harden. 50 cc. of hot agar was added to50 cc. of the above toxic agar to give a sulfide concentration of 0.05

growth of Aspergillus niger are effective in explaced 0.1 gram of thesulfide.

per cent. To 10 cc. of the remaining toxic agar was added 90 cc. of agarto give a concentration of 0.005 per cent. Petri plates were poured fromeach of the two mixtures, i. e., that having a 2-hydroxyethylZ-phenylethyl sulfide concentration of "0.05 perfcent and that having an0.005 per cent-concentration. The plates were then sprayed withAspergillus wider and incubated at a temperature of 28 C. for five days.At the end of that time inspection of the plates showed that on platesof both the 0.05 percent and 0.005 per cent concentration the growth ofAspe'rgz'llus m'ger was completely inhibited. 1

Similarly good results against this organismare obtained by employingother hydroxyalkyl Z-phenylethyl sulfides or the chloro, bromo or 4.material which is to be treated. Generally the halogen free sulfides arepreferred when phytocidal action is to be avoided.

What I claim is:

l. The method of protecting organic material susceptible to attack byfungi which comprises applying to said organic material a fungicidalcomposition comprising Z-hydroxyethyl 2- phenylethyl sulfide.

- 2. The method of destroying fungus which comprises applying2-hydroxyethyl Z-phenylethyl sulfide to said fungus.

fiuoro derivatives thereof, e. g., 4-hydroxybutyl v Z-phenylethylsulfide, Z-hydroxyethyl 2-(2,3-dichlorophenyl) ethyl sulfide, and2-hydroxypropyl The present sulfides may also be employed as fungicidesagainst the following organisms: Sclefotinza fructiola, Trychophytoninterdzgitale, T. Rubrum, C. Albz'cans, Stemphyllium sarcinoformae, etc.The choice of the particular sulfide employed depends somewhat upon theorganic v v JOACI-HM DAZZI.

RcferencesCi ted in the file of this patent V FOREIGN PATENTS NumberCountry Date 665,371 Germany Sept. 24, 1938 532,676 Great Britain Jan.29, 1941 363,656 Germany Nov. 11, 1922 OTHER REFERENCES lioskins et al.:Journal of Economic Entomol ogy, volume 33, Number 6, December 1940,pages

1. THE METHOD OF PROTECTING ORGANIC MATERIAL SUSCEPTIBLE TO ATTACK BYFUNGI WHICH COMPRISES APPLYING TO SAID ORGANIC MATERIAL A FUNGICIDALCOMPOSITION COMPRISING 2-HYDROXYETHYL 2PHENYLETHYL SULFIDE.